The present invention relates generally to the field of electrochemical cells. More particularly, this invention pertains to lithium batteries in which the cathode comprises an electroactive sulfur-containing material and the cathode current collector comprises a conductive support and a crosslinked polymeric conductive primer layer.
Throughout this application, various publications, patents, and published patent applications are referred to by an identifying citation. The disclosures of the publications, patents, and published patent specifications referenced in this application are hereby incorporated by reference into the present disclosure to more fully describe the state of the art to which this invention pertains.
As consumer demand for, and reliance upon, portable and hand-held electronic devices such as mobile telephones, portable computers, pagers and palm pilots has grown, so has the need for portable power supplies, such as rechargeable batteries, with long cycle life, rapid recharge capacity, and high energy density become more important. There has been considerable interest in recent years in developing high energy density primary and secondary batteries with alkali-metal anode materials, and, in particular, anodes based on lithium.
One component of a battery, especially a rechargeable battery, which is important for long cycle life, rapid charge capacity, and high energy density, is the current collector. In rechargeable lithium batteries, for example, current collectors have typically been constructed of nickel or aluminum. Aluminum is generally preferred due to lower cost and lower density. Unfortunately, current collectors constructed from aluminum exhibit a relatively high interfacial impedance associated with the presence of an oxide layer on the surface, which, in turn, results in a loss of energy and reduced power. Such losses are generally attributed to the fact that the aluminum surface includes a native oxide layer which (a) acts as an insulator, increasing interfacial impedance, and thus severely limits electrical conductivity, and (b) greatly hinders adhesion of electrochemically active electrode materials which are to be applied to the surface of the aluminum current collector during electrode fabrication.
Two approaches have been presented to improve aluminum current collector functioning. One approach emphasizes primer layers on the aluminum with improved adhesion, and a second approach emphasizes reduction of interfacial resistance at the aluminum interface. In the first approach, polymers containing carboxylic acid functionality have been found to provide strong adhesion to aluminum metal surfaces. For example, in U.S. Pat. No. 5,827,615, Touhsaent et al. show that adhesion of polyvinyl alcohol polymers to aluminum films is improved by the use of carboxylic acid containing polymers in the formulation, such as olefin-maleic acid copolymers. Chassar et al., in U.S. Pat. No. 6,069,221, report that a carboxylic acid function in polymer formulations improves adhesion to metals, particularly aluminum. Similarly, in U.S. Pat. Nos. 5,441,830 and 5,464,707 to Moulton et al., the adhesion-promoting properties of carboxylic acid functionality is described in an electrically conducting primer layer material. In U.S. Pat. Nos. 5,399,447 and 5,520,850 to Chaloner-Gill et al. is described an adhesion promoting layer containing conducting material and a polymer, such as a polyacrylic acid, and a lithium salt to reduce acidity and reactivity to a lithium anode. An example of a conductive primer layer for a current collector from a crosslinked polymer from a crosslinking reaction of a polymer having pendant carboxyl groups, such as ethylene/acrylic acid polymers, with a multifunctional crosslinking agent, is described in U.S. Pat. No. 5,478,676 to Turi et al.
Improved current collector performance by reduction of interfacial resistance has been described, for example, in U.S. Pat. Nos. 5,578,396, 5,591,544, and 5,588,971 to Fauteux et al., by freeing the surface of an aluminum current collector of oxide, etching the surface with a carboxylic acid material to improve adhesion, and providing a primer, such as graphite, to prevent re-growth of the oxide layer. Although carboxylic acid polymers may provide excellent adhesion to aluminum current collectors, problems of corrosion of the aluminum by cell components may still exist.
Another approach to reduce the corrosion of aluminum current collectors is described in U.S. Pat. No. 5,518,839, to Olsen, in which a layer of a corrosion resistant metal, such as nickel, copper, chromium, titanium, or mixtures thereof, is applied to an etched aluminum current collector surface. Such an approach, however, adds an additional process step and adds weight and cost to the cell.
It is thus an object of the present invention to provide a current collector and method of manufacturing same, wherein the current collector has a substantially reduced interfacial impedance and substantially increased adhesive capabilities.
The cathode current collector of the present invention for use in an electrochemical cell comprises: (a) a conductive support, and (b) a conductive primer layer overlying the conductive support, wherein the primer layer comprises from about 20 to 60% by weight of a crosslinked polymeric material formed from a reaction of a polymeric material having hydroxyl groups and a crosslinking agent, about 2 to 15% by weight of a cationic polymer comprising quaternary ammonium salt groups, and about 35 to 75% by weight of a conductive filler. In a preferred embodiment, the cell comprises: (i) an anode comprising lithium, and (ii) a cathode comprising an electroactive sulfur-containing material.
Suitable polymeric materials having hydroxyl groups include, but are not limited to, polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, vinyl acetate-vinyl alcohol copolymers, ethylene-vinyl alcohol copolymers, and vinyl alcohol-methyl methacrylate copolymers. The crosslinking agent is preferably selected from the group consisting of phenolic resins, epoxides, melamine resins, polyisocyanates, and dialdehydes. The cationic polymer comprising quaternary ammonium salt groups is preferably selected from the group consisting of poly(diallyldimethylammonium) salts, copolymers of acrylamide and diallyldimethylammonium salts, copolymers of diacetone acrylamide and diallyldimethylammonium salts, copolymers of N-methylolacrylamide and diallyldimethylammonium salts, polyvinyl benzyl trimethyl ammonium salts, salts of polyepichlorohydrin quaternized with trimethyl amine, polymethacrylamidopropyltrimethyl ammonium salts, polymethacryloyloxyethyltrimethyl ammonium salts, and polymethacryloyloxyethyl dimethyl hydroxyethyl ammonium salts. The conductive filler is preferably selected from the group consisting of carbon black, graphites, activated carbon fibers, non-activated carbon nanofibers, metal flakes, metal powders, and electrically conductive polymers. The conductive support is preferably selected from the group consisting of aluminum foil and aluminized plastic films.
In one embodiment of the present invention, the weight ratio of the polymeric material having hydroxyl groups to the crosslinking agent in the crosslinked polymeric material is from 10:1 to 2:1. Preferably, the thickness of the conductive primer layer is from about 0.2 to 5 microns.
In one embodiment, the electroactive sulfur-containing material comprises elemental sulfur. In another embodiment, the electroactive sulfur-containing material, in its oxidized state, comprises a polysulfide moiety of the formula, Sm, wherein m is an integer equal to or greater than 3. In yet another embodiment, the electroactive sulfur-containing material comprises a sulfur-containing organic polymer.
Another aspect of the present invention pertains to methods of preparing a cathode current collector of an electrochemical cell, wherein the current collector, as described herein, is formed by the steps of: (a) coating onto a conductive support a liquid mixture comprising a polymeric material having hydroxyl groups, a crosslinking agent, a cationic polymer comprising quaternary ammonium salt groups, a conductive filler, and a liquid medium; and (b) drying and crosslinking the coating formed in step (a) to yield the current collector. The drying and crosslinking step (b) is preferably performed at a temperature of from about 60xc2x0 C. to about 170xc2x0 C.
In one embodiment, the liquid medium comprises water. In another embodiment, the liquid medium comprises one or more organic solvents.